Combined fungicidal and insecticidal spray materials



Patented June 23, 1936 COMBINED FUNGICIDAL AND lNSECTICIDAL SPRAYMATERIALS Wendell H. Tisdale, Wilmington, Del., and Louis 8. Bake,Pennsgrove, N. J., assignors to E. I. du Pont de Nemours 8; Company,Wilmington, Del., a corporation of Delaware No Drawing. ApplicationSeptember 2, 1932,

Serial No.

13 Claims.

This invention relates to combined fungicidal and insecticidal materialsand particularly to oil emulsions adapted for spraying plants infestedwith fungi and scale insects.

For many years there has been a recognized need for more effectivecombined fungicide and insecticide spray materials. This is especiallytrue of material for sprays for use on citrus trees where scale insectsand parasitic fungi are active fungicidal properties, composed of astable oil or oils, a penetrating and solvent agent, and a mercurycompound having fungicidal properties and which is soluble in at leastone of the constituents of the spray material. The use of emulsifiedoils for the control of scale insects is well known. Also the use ofmercury compounds for the control of bacterial and fungus diseases isestablished.

Our invention is based upon the discovery that V10 all year round. Manymaterials have been proposed for this purpose but have not proved to bethe insecticidal properties of oils are augmented entirely satisfactory.Some of these spray mateby the'presence, of mercury compounds. The rialswhich have been employed up to the present mercury compounds, whenemployed in these oil time and particularly the oil emulsion sprays tendmixtures, are more effective for our purpose than 5 to injure thefoliage of growing plants; some when employed in any other spraycombination 15 carry insoluble particles which break the oil filmheretofore known. These oil-mercury combinaand reduce the effectivenessof the oil on the scale tions are especially suited to the control ofscale insects; some fail to control one or more of the insects andfungus diseases of citrus trees 91- parasites; and some frequentlypermit the growth though they may be used on other plants.

of one or more of the parasites to become more In carrying out ourinvention the oil or com- 20 rapid after use than before. This latterdisadbination of oils employed are of sufficient purity vantage isparticularly true of the copper and oil to be non-injurious to theplants when used in sprays as the copper salts remain on the leaves thedesired concentration for spraying. Oils of of the plant for a longperiod of time after applisufilciently low viscosity to spread andpenetrate cation and prevent the recurrence and spread of well and atthe same time volatilize within a 25 the so-called "friendly fungi buthave no effect reasonable time after application are preferred. on thescale insects. Accordingly the recurrence It is known that emu fi d 0 avViscosity in growth of scale insects after the application of below 80Saybolt tend to penetrate the leaf tissue such copper and oil sprays isusually much greater and cause injury (GuinsburgJour. Agr. Res. vol.

than before such treatment. 43 No. 5, 1931). Oils having a viscosityabove 30 The sulfur and oil sprays have also been used 100 saybolt a e ky to c use j y y P d cwith some degree of success but on the whole ing asmothering effect and are not as effective have proved unsatisfactorydue to injury caused n the Co f 8 O having a lower to the plant or lackof control of one or more of viscosity. Accordingly, we prefer to employoils the parasites. having a viscosity between 80100 Saybolt, al-

," An object of our invention is to provide new though W c nsider s o nWithin 11 invenand more effective compositions of matter which tion oilsof higher or lower viscosity. The proper are adapted to be used forspraying citrus trees viscosity maybe obtained by mixing one or more andother plants. Further objects are to provide oils of differentviscosity. Some of the parafiin 40 spray materials of the above typewhich have a oils are well suited for this purpose. 40 less tendency toinjure the foliage of growing In order to make the oil or oils moreeffective plants, carry no insoluble particles to break the in killingscale insects we contemplate employing oil film, exert a high degree ofcontrol upon both penetrating or solvent agents with the oils. Such thescale and parasitic fungi, and do not prevent solvent or penetratingagents should be comthe spread and multiplication of the friendlypatible with the oil and mercury compounds and 45 fungi. A still furtherobject is to provide a new harmless to plants in the strengths employed.process of treating plants infested with parasitic Among the penetratingand solvent agents which fungi and scale insects. Other objects are towe have found to be particularly satisfactory for provide newcompositions of matter and to adour purpose are pine oil, mono-ethylether of Vance the art. Still other objects will appear ethylene glycol,b-bedichloro-diethyl-ether. 50 hereinafter. However, our invention isnot to be limited to the These objects may be accomplished in accorduseof these particular penetrating and solvent ance with our inventionwhich comprises spraying agents as many similar materials may beeminfested plants with water containing a composiployed to advantage insuch sprays.

tion of matter having combined insecticidal and The mercury compoundswhich we have found larly satisfactory are ethyl-mercury-chloride andsome of the oil soluble hydrocarbon mercury salts disclosed in acopending application, Serial No. 625,526, filed on or about July 28,1932, Patent No. 1,993,776. These oil soluble mercury compounds may beadded as such to the oil or may be prepared by reacting the ingredientsin the 011. They are carried in the oil when the mixture is emulsifiedand are spread on the foliage and held in place by the oil. While theoil soluble mercury compounds are preferred, we have also found that oilinsoluble mercury salts may be employed so long as such mercury salts orcompounds are soluble in at least one of the other constituents of thespray. While the oil insoluble mercury compounds which are soluble inone of the other constituents of the spray may be employed generally, wepreferably employ the less volatile compounds under such conditions.Among the oil insoluble mercury compounds which we have found to beparticularly satisfactory for our purpose are ethyl-mercury-phosphateand ethylmercury-arsenate which are water soluble in the presence of analkali and thus can be introduced into the emulsion by mixing with analkaline emulsifying agent which is dissolved in the water before addingthe oil.

Our oil-mercury combinations may be emulsified by any of the commonlyaccepted methods employed for emulsifying oils. The emulsion may be madein concentrated form and later diluted for application, or the emulsionmay be made in the final dilution at the time of application. For thispurpose, the emulsifying agent may be added to the oil in advance, ifsoluble, or added when the emulsion is prepared.

In order to more fully illustrate our invention and the preferred modeof carrying the same into effect, the following examples are given ofvarious compositions and methods of making the same, which may bediluted so as to contain from about 0.52% of oil to be employed forspraying purposes:

Example 1.6.85 grams of HgClz and 4.2 grams of lead tetraethyl wereadded to /2 gallon of a mixture of transformer oil and 10% pine oil andthe mixture warmed until the reaction was complete. The lead diethyldichloride formed in the reaction was filtered off and 136 grams ofoleic acid was added to the filtrate containing the ethyl mercurychloride in solution, which was then emulsified with gallon of water.containing 58 grams of triethanolamine.

This emulsion, when diluted in water to contain 1% of oil, was found tobe very effective in the control of red scale, purple scale, scab(Sphaceloma) and Melanose (Phomopsis citri) of citrus trees. It waslikewise found effective in the control of blue stain or sap stain oflumber.

The oleic acid and triethanolamine operate primarily as emulsifyingagents.

Example 2.-'l4.4 grams of'mercuric chloride and 46.0 grams of lead tetraethyl were added to 20 pounds of a mixture of 48% of 65 paraflin oil,48% 110 paraifin oil, and 4% pine oil and heated until the reaction wascomplete. The lead diethyl dichloride formed in the reaction wasfiltered off and 3 pounds of oleic acid were added to the filtrate,containing the ethyl mercury chloride in solution, which was thendiluted to 40 pounds with the paraffin oils and pine oil in the abovementioned proportions. This oil is now ready for emulslfication with thedesired quantity of water containing from -150 grams of sodium resinateper gallon of oil to be emulsifled. Soda ash itself may be substitutedfor the sodium resinate. This emulsion gave essentially the same resultas Example 1. The sodium resinate functions as an emulsifying andspreading agent and the oleic acid aids in the emulsification.

Example 3.-100 grams of a mixture of 48% of 65 paraffln oil, 48% ofparamn oil and 4% pine oil, containing 0.4% of ethyl mercury chloride,prepared in a manner similar to the procedure stated in Example 1, i. e.by formation of the ethyl mercury chloride in the oil by reacting theingredients therein and then separation of the lead diethyl dichloride,was diluted with 5 grams of butyl ammonium oleate as an emulsifyingagent. The resulting oil is very rapidly emulsified by adding anydesired amount to water and agitating.

Example 4.-A composition, similar to that of Example 2, was prepared bysubstituting the monoethyl-ether of ethylene glycol for the pine oil,otherwise employing ,the ingredients and process of Example 2.

Example 5.-A composition, similar to that of Example 2, was prepared bysubstituting b-bdichloro-diethyl-ether for the pine oil of Example 2,otherwise proceeding substantially as described in Example 2.

Example 6.A concentrated solution of ethyl mercury oleate was preparedas follows:

111.0 grams of mercuric oxide, 375 cc. of oleic acid, and 81 grams oflead tetra ethyl were added to 500 cc. of 65 paraffin oil, the mixtureheated until the reaction was complete and then diluted to 2250 cc. with65 paraffin oil.

840 cc. of the above concentrate was diluted with 660 cc. pine oil, 6280cc. of 110 paraflin oil,

5460 cc. of 65 paraffin oil and 4410 cc. of oleic acid. This oil can bereadily emulsified by mixing 1 gallon with, say, '72 gallons of watercontaining grams of sodium resinate (described in Example 2) or anapproximate equivalent amount of sodium carbonate.

Example 7.-The procedure of Example 6 was followed except that stearicacid was substituted for the oleic acid of such exainple, therebyproducing an emulsion containing ethyl mercury stearate.

Example 8.-An emulsion containing ethyl mercury palmitate was preparedby following the process of Example 6 but substituting the molecularequivalent of palmitic acid for the oleic acid of Example 6.

Example 9.--2315 grams of soda ash, 107.5 grams of mercuric chloride and35 grams of lead tetra ethyl were introduced into a ball mill and milleduntil the reaction between the mercuric chloride and lead tetra ethylwas complete. The

spray emulsion was made by dissolving the re- 35 phosphoric acid and91.8 grams of lead tetra 75 i in which R. is

ethyl were added to a ball mill and the mix milled until th oleic acidas in Example Emample 11. grams This radical and X an an unsubstitutedhydrocarbon acid radical.

Some of the comin which R is an unsubs described in the Kharaschapplications flied on or about May 26, 1930 and No.

tituted hydrocarbon as 276,189, filed on or about May 8, 1928,respectively; mercury salts of in Kharasch application No.

monoamines described 408,676, filed on or ture Dosed sitic fungi to beobtained, the scale insects but do not r nce of the friendly fungi.

and spread of the so-called While we have disclosed ofparticularcompositions comsubstances inspecific compound being constituents of theemulsion.

3. A composition of matter said compound the constituents 4. Acomposition of matter suitable for use as an insecticide and fungicidewhich compound being soluble in the 0' 7. A composition uninsecticideand fungicide which comprises an oil emulsion containing a compoundhaving the formula:

R-HK-X wherein R represents an unsubstituted hydrocarbon radical and 1:represents an acid radical. 10. A composition of matter suitable for useas an insecticide and fungicide which comprises an an insecticide andfungicide which comprises an oil emulsion containing a. compound havingthe formula:

nan-1:

9. A" composition of matter suitable for use as V wherein"t representsan unsubstituted hydrocarbon rs a1 and X represents a. radical of afatty acid.

12. A composition of matter suitable for use as aninsecticide andfungicide which comprises an oil emulsion containing ethyl mercurystearate.

13. A composition of matter suitable for use as an insecticide andfungicide which comprises an oil emulsion containing ethyl mercurypalmitate.

WENDEIL H. TISDALE. LOUIS S. BAKE.

